EP0470180B1 - Poly(amide ether) hydroxy-fonctionnels utilises en tant que resine thermoplastique a effet barriere - Google Patents

Poly(amide ether) hydroxy-fonctionnels utilises en tant que resine thermoplastique a effet barriere Download PDF

Info

Publication number
EP0470180B1
EP0470180B1 EP90907828A EP90907828A EP0470180B1 EP 0470180 B1 EP0470180 B1 EP 0470180B1 EP 90907828 A EP90907828 A EP 90907828A EP 90907828 A EP90907828 A EP 90907828A EP 0470180 B1 EP0470180 B1 EP 0470180B1
Authority
EP
European Patent Office
Prior art keywords
polymer
moiety
hydrogen
arylene
carbons
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP90907828A
Other languages
German (de)
English (en)
Other versions
EP0470180A4 (en
EP0470180A1 (fr
Inventor
Jerry E. White
David J. Brennan
Steven Pikulin
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dow Chemical Co
Original Assignee
Dow Chemical Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=23351308&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP0470180(B1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Dow Chemical Co filed Critical Dow Chemical Co
Publication of EP0470180A1 publication Critical patent/EP0470180A1/fr
Publication of EP0470180A4 publication Critical patent/EP0470180A4/en
Application granted granted Critical
Publication of EP0470180B1 publication Critical patent/EP0470180B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/62—Alcohols or phenols
    • C08G59/621—Phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • C08G59/28—Di-epoxy compounds containing acyclic nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/40—Polyamides containing oxygen in the form of ether groups

Definitions

  • This invention relates to thermoplastic polymers having pendant hydroxyl moieties and aromatic ether moieties and to articles prepared from such polymers.
  • Hydroxyphenoxyether polymers are known to be useful in the fabrication of articles exhibiting barrier properties. See, for example, Reinking et al, J.Poly Sci., Vol. 7, pp. 2135-2144, pp. 2145-2152 and pp. 2153--2160 (1963) and Encyclopedia of Polymer Science and Technology, Vol. 10, pp. 111-122. Such polymers generally have only moderate oxygen barrier, i.e., they generally exhibit oxygen transmission rates of 2 or more and up to 75 cm 3 -mil/100 in 2 -atm-day (0,9-30 cm 3 /mm/m 2 - atm - day).
  • US-A-3948855 discloses thermoplastic pherolic hydroxyethers containing amide moieties and pendant hydroxyl moieties.
  • US-A-3637590 discloses polyether resins for high impact applications, incorporating a dihydric polynuclear pherol.
  • the present invention provides a thermoplastic polymer which is solid at temperatures in the range of 15 to 35°C, and which has repeating units represented by the formula: wherein each Ar 1 is independently a divalent aromatic moiety, each R 1 is a divalent radical of which at least 50 percent by weight is hydrocarbon each R 2 is independently a monovalent aliphatic moiety, and each R 3 is independently is a divalent radical of which at least 50 percent by weight is hydrocarbon.
  • the polymer of this invention hereinafter called a hydroxy-functional poly(amide-ether), exhibits thermoplastic character and excellent barrier to oxygen in both dry and moist environments.
  • the polymer can be extruded, molded or fabricated by other heat plastifying methods to form a variety of articles such as films, bags and tubes as well as stand alone containers. Such polymers retain their thermoplasticity even after being subjected to such heat plastifying conditions.
  • "normally solid” it is meant that the polymer is solid at ambient temperatures, eg. 15 to 35°C.
  • this invention is a container suitable for packaging oxygen-sensitive materials wherein the container is fabricated of the hydroxy-functional poly(amide-ether). In yet a further aspect, this invention is a substantially impermeable film or coating of the polymer.
  • the polymers of this invention are also useful as molding, extrusion and casting resins.
  • the hydroxy-functional poly(amide-ether) has repeating units represented by the formula: wherein each Ar 1 is independently a divalent aromatic moiety, each R 1 is a predominantly hydrocarbylene moiety, each R 2 is independently hydrogen or a monovalent aliphatic moiety, and each R 3 is independently a predominantly hydrocarbylene moiety.
  • the nitrogen atom of the amide moiety is bonded to an aromatic ring.
  • "Predominantly hydrocarbylene" is defined as a divalent radical of which at least 50 percent by weight is hydrocarbon, but which optionally contains a minor amount of heteroatomic moiety such as oxygen, sulfur, imino, sulfonyl, sulfoxyl and the like.
  • hydroxy-functional poly(amide-ethers) of this invention are more preferably those represented by the formula: wherein Ar 1 , R 1 , R 2 and R 3 are as defined before, Y is hydrogen or a monovalent organic terminating group, Z is a monovalent organic terminating group, and n is a whole number from 10 to 1000.
  • R 1 is a predominantly hydrocarbylene such as (1) alkylene which has from 1 to 10 carbons which may contain a heteroatomic moiety such oxygen, sulfur, sulfonyl or sulfoxyl and (2) arylene which has from 5 to 25 carbons, may contain a heteroatomic moiety and may be substituted with alkyl, alkoxy, halo, nitro or cycloalkyl groups.
  • R 2 is hydrogen or a hydrocarbyl or substituted hydrocarbyl wherein hydrocarbyl is a monovalent hydrocarbon such as alkyl, cycloalkyl, aralkyl, or aryl and the substituent(s) is a monovalent moiety which is inert in the reactions used to prepare the hydroxy-functional poly(amide-ether).
  • R 3 while usually different from R 1 , is similarly a predominantly hydrocarbylene moiety as previously defined.
  • Ar 1 is arylene or substituted arylene wherein the substituent may be alkyl, alkoxy, halo, nitro or cyano.
  • Y is hydrogen or Z is or and n is a whole number from 10 to 1000.
  • R 1 is (1) alkylene having from 1 to 10 carbons such as n-butylene, n-pentylene, n-hexylene, n-octylene; (2) alkyleneoxyalkylene such as ethyleneoxyethylene; (3) alkylenethioalkylene such as ethylenethioethylene or alkylenesulfonylalkylene such as ethylenesulfonylethylene; (4) alkyleneoxyaryloxyalkylene such as ethyleneoxyphenoxyethylene; (5) alkylenearylalkylene such as methylenephenylmethylene; or (6) arylene such as phenylene or substituted arylene such as halophenylene.
  • R 1 groups n-butylene is especially preferred.
  • R 2 is hydrogen or alkyl having from 1 to 4 carbons such as methyl, ethyl, propyl and butyl, with hydrogen being especially preferred.
  • R 3 is most preferably arylene such as phenylene, biphenylene, or naphthenylene; bisphenylenealkylidene such as bisphenyleneisopropylidene, bisphenylenecyanomethane and bisphenylenemethane; bisphenyleneoxide; or bis-(phenyleneamido)alkane such as bis(phenyleneamido)butane, bisphenylene sulfide, bisphenylene sulfone, bisphenylene ketone and bisphenylene amide, with bisphenyleneisopropylidene being especially preferred.
  • Ar 1 is most preferably phenylene or substituted phenylene wherein the substituent is alkyl, halo or nitro, with phenylene
  • the hydroxy-functional poly(amide-ethers) are preferably prepared by contacting a N,N'-bis(hydroxyphenylamido)alkane or arene, hereinafter referred to as a dihydroxyl diamide, with a diepoxide under conditions sufficient to cause the hydroxyl moieties to react with epoxy moieties to form ether linkages, and pendant hydroxyl moieties.
  • the amide moieties do not react with the epoxy groups to form any significant cross-linkages.
  • Conditions conventionally employed in the reaction of epoxides with phenols to form ether linkages are suitably employed in preparing the resins of this invention.
  • the process for preparation is carried out so that the unreacted epoxy groups in the finished polyether are minimized.
  • the epoxy groups in the polyether By minimizing the epoxy groups in the polyether, the essential thermoplastic character of the polymer can be retained. Preferred conditions for preparing such resins are set forth in the following working examples.
  • the dihydroxyl diamide is prepared by contacting a suitable diacid or diacid halide with a substantial excess of an aminoarenol under conditions sufficient to cause reaction of the amine moieties with the acid halide moieties to form amide moieties.
  • diacids and diacid halides that are suitably employed include acids and acid halides, preferably chlorides, of the following acids: oxalic, adipic, malonic, succinic, glutaric, fumaric, maleic, pimelic, suberic, azelaic, sebacic, terephthalic, and isophthalic.
  • aminoarenols suitably employed include the following: aminophenols such as p-aminophenol and m-aminophenol, aminonaphthols and other aminohydroxyarenes.
  • Conditions conventionally employed for the reaction of acid chlorides with amines to form amides are suitably employed to form the dihydroxyl diamides of this invention. Examples of such suitable conditions are set forth according to J. Preston, J.Polym.Sci., Vol. 8, p. 3135-3144(1970). Preferred conditions for preparing the dihydroxyl diamides are set forth hereinafter in the working examples.
  • diepoxides include the diglycidyl ethers of dihydric phenols such as 4,4'-isopropylidene bisphenol (Bisphenol A), 4,4'-dihydroxydiphenylethylmethane, 3,3'-dihydroxydiphenyldiethylmethane, 3,4'-dihydroxydiphenylmethylpropylmethane, bisphenol, 4,4'-dihydroxydiphenyloxide, 4,4'-dihydroxydiphenylcyanomethane, 4,4'-dihydroxybiphenyl, 4,4'-dihydroxybenzophenone, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl sulfone, 2,6-dihydroxynaphthalene, 1,4'-dihydroxynaphthalene, hydroquinone, resorcinol, catechol and other dihydric phenols listed in US-A-4,438,254 and 4,
  • the term "barrier polymers” means that the polymer exhibits an oxygen transmission rate which is less than 5, preferably less than 1 and most preferably less than 0.5 cubic centimeters/mil/100 inch 2 /atmosphere/day (2, 0.4, and 0.2 cm 3 /mm/m 2 - atm - day respectively).
  • the barrier properties of the polymer can be significantly affected by the mole ratios of amide moieties to pendent hydroxyl moieties.
  • this mole ratio of amide to hydroxyl is at least 1:10, more preferably at least 1:2 and most preferably about 1:1.
  • barrier containers, films and coatings of this invention are fabricated from the poly(amide-ether) using conventional fabricating techniques for normally solid, thermoplastio polymers such as extrusion, compression molding, injection molding and similar fabrication techniques commonly employed to produce such articles.
  • a 10.5-g (31.98 mmoles) portion of the adipamide of Part A and diglycidyl ether of Bisphenol A (DGBA) (11.26 g, 32.62 mmoles, epoxy equivalent weight of 172.58) in 13 mL of freshly distilled propylene glycol phenylether are heated with stirring to 140°C-150°C under a nitrogen atmosphere.
  • the diglycidyl ether is recrystallized from methanol twice before use. About 15-20 drops of ethyltriphenylphosphonium acetate (70 percent in methanol) are added as the catalyst and, after a brief induction period, the temperature of the reaction rises to 160°C-170°C with complete dissolution of the monomers.
  • reaction solution is maintained at 150°C-160°C for 20 minutes and then cooled to 100°C and diluted with 25 mL of dimethylformamide (DMF).
  • DMF dimethylformamide
  • the resulting solution is poured into a rapidly stirred 1:1 methanol/water mixture (400-600 mL) to precipitate the product which is then redissolved in DMF (50 mL) and reprecipitated from the methanol/water mixture.
  • Specimens (10 cm x 10 cm x 0.013 cm) for oxygen barrier evaluations are prepared by compression molding samples (3.5 g) of the polymer of Part B between Teflon sheets in a brass template at 200°C at 500 psi (3.5 mPa) for 8-10 minutes, then at 40,000 psi (275 mPa) for 2-4 minutes and then cooled at 40,000 psi for 10 minutes. Oxygen transmission rates are then measured for the samples and the results are reported in Table I.
  • the polymers of this invention exhibit excellent barrier to oxygen transmission in a wet environment as well as in a dry environment.

Abstract

Des poly(amides-éthers) hydroxy-fonctionnels sont utilisés pour la fabrication d'articles tels que des conteneurs rigides et des films flexibles ayant un effet barrière prononcé à la transmission d'oxygène tant dans des environnements secs que dans des environnements humides. Par exemple, un polymère préparé en faisant réagir le diglycidyl-éther de 4,4'-biphénole avec N,N'-bis(m-hydroxyphényl)-adipamide a un effet barrière particulièrement prononcé.

Claims (7)

  1. Polymère thermoplastique qui est solide aux températures situées dans l'intervalle allant de 15°C à 35°C et qui comporte des motifs répétés de formule
    Figure imgb0027
     dans laquelle chaque Ar1 représente indépendamment un groupe aromatique divalent, chaque R1 représente un groupe divalent, hydrocarboné pour au moins 50 % en poids, chaque R2 représente indépendamment un groupe aliphatique monovalent, et chaque R3 représente indépendamment un groupe divalent, hydrocarboné pour au moins 50 % en poids.
  2. Polymère conforme à la revendication 1, de formule
    Figure imgb0028
     dans laquelle chacun des symboles Ar1, R1, R2 et R3 a la définition indiquée dans la revendication 1, Y représente un atome d'hydrogène ou un groupe organique monovalent de terminaison, Z représente un groupe monovalent de terminaison, et n représente un nombre enticr qui vaut de 10 à 1000.
  3. Polymère conforme à la revendication 2, dans lequel R1 représente
    1) un groupe alkylène comportant de 1 à 10 atomes de carbone, ou un groupe hétéroalkylène comportant un groupe alkylène et un maillon hétéroatomique qui est un atome d'oxygène ou dc soufre ou un groupe sulfonyle ou sulfoxyle, ou bien
    2) un groupe arylène comportant de 5 à 25 atomes de carbone, qui contient éventuellement un maillon hétéroatomique et qui peut éventuellement porter un ou des substituants alkyle, alcoxy, halogéno, nitro ou cyano,
    R2 représente un atome d'hydrogène ou un groupe hydrocarbyle portant ou non, en tant que substituants, un ou des groupes monovalents qui restent inertes au cours des réactions mises en oeuvre pour préparer le polymère,
    R3 représente
    1) un groupe alkylène comportant de 1 à 10 atomes de carbone, ou un groupe hétéroalkylène comportant un groupe alkylène et un maillon hétéroatomique qui est un atome d'oxygène ou de soufre ou un groupe sulfonyle ou sulfoxyle, ou bien
    2) un groupe arylène comportant de 5 à 25 atomes de carbone, ou un groupe hétéroarylène comportant un cycle arylène interrompu par l'un desdits maillons hétéroatomiques,
    Ar1 représente un groupe arylène portant ou non un ou des substituants alkyle, alcoxy, halogéno, nitro ou cyano,
    Y représente un atome d'hydrogène ou un groupe de formule
    Figure imgb0029
    et Z représente un groupe de formule
    Figure imgb0030
     ou
    Figure imgb0031
  4. Polymère conforme à la revendication 3, dans lequel R1 représente un groupe n-butylène, R2 représente un atome d'hydrogène, R3 représente un groupe bis(phénylène)isopropylidène, Ar1 représente un groupe phénylène, Y représente un atome d'hydrogène, et n représente un nombre valant de 100 à 400.
  5. Récipient à propriétés de barrière, formé d'un polymère conforme à l'une des revendications 1 à 4.
  6. Film à propriétés de barrière, formé d'un polymère conforme à l'une des revendications 1 à 4.
  7. Procédé de préparation d'un polymère conforme à l'une des revendications 1 à 4, qui comporte le fait de mettre un N,N'-bis(hydroxyarylamido)hydrocarbylène en contact avec un diépoxyde, dans des conditions suffisantes pour que les groupes hydroxyles réagissent avec les groupes époxy et forment ainsi le polymère.
EP90907828A 1989-04-26 1990-04-26 Poly(amide ether) hydroxy-fonctionnels utilises en tant que resine thermoplastique a effet barriere Expired - Lifetime EP0470180B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US34463089A 1989-04-26 1989-04-26
US344630 1989-04-26
PCT/US1990/002312 WO1990012828A1 (fr) 1989-04-26 1990-04-26 Poly(amide ether) hydroxy-fonctionnels utilises en tant que resine thermoplastique a effet barriere

Publications (3)

Publication Number Publication Date
EP0470180A1 EP0470180A1 (fr) 1992-02-12
EP0470180A4 EP0470180A4 (en) 1992-07-15
EP0470180B1 true EP0470180B1 (fr) 1997-03-05

Family

ID=23351308

Family Applications (1)

Application Number Title Priority Date Filing Date
EP90907828A Expired - Lifetime EP0470180B1 (fr) 1989-04-26 1990-04-26 Poly(amide ether) hydroxy-fonctionnels utilises en tant que resine thermoplastique a effet barriere

Country Status (8)

Country Link
EP (1) EP0470180B1 (fr)
JP (1) JPH08509506A (fr)
KR (1) KR920701296A (fr)
AU (1) AU650621B2 (fr)
BR (1) BR9007322A (fr)
CA (1) CA2051446A1 (fr)
DE (1) DE69030084T2 (fr)
WO (1) WO1990012828A1 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5134218A (en) * 1991-06-06 1992-07-28 The Dow Chemical Company Hydroxy-functional poly(amide ethers) as thermoplastic barrier resins
JP2001501248A (ja) * 1996-09-30 2001-01-30 ザ・ダウ・ケミカル・カンパニー ヒドロキシ―フェノキシエーテルポリマー熱可塑性複合体

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4367328A (en) * 1981-03-05 1983-01-04 The Dow Chemical Company Epoxy resins from hydroxy benzamides

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3477990A (en) * 1967-12-07 1969-11-11 Shell Oil Co Process for reacting a phenol with an epoxy compound and resulting products
US3637590A (en) * 1970-03-31 1972-01-25 Russel L Maycock Thermoplastic polyether resins of bisphenols
US3948855A (en) * 1971-09-16 1976-04-06 The Dow Chemical Company Process for reacting a phenol with a vicinal epoxy compound in the presence of phosphorus or carbon containing acid, ester or acid ester

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4367328A (en) * 1981-03-05 1983-01-04 The Dow Chemical Company Epoxy resins from hydroxy benzamides

Also Published As

Publication number Publication date
WO1990012828A1 (fr) 1990-11-01
AU5563590A (en) 1990-11-16
DE69030084D1 (de) 1997-04-10
EP0470180A4 (en) 1992-07-15
AU650621B2 (en) 1994-06-30
KR920701296A (ko) 1992-08-11
JPH08509506A (ja) 1996-10-08
DE69030084T2 (de) 1997-09-25
BR9007322A (pt) 1992-04-21
CA2051446A1 (fr) 1990-10-28
EP0470180A1 (fr) 1992-02-12

Similar Documents

Publication Publication Date Title
US5089588A (en) Hydroxy-functional poly(amide ethers) as thermoplastic barrier resins
US5143998A (en) Hydroxy-functional poly(amide ethers) as thermoplastic barrier resins
EP0542972B1 (fr) Poly(ethers-amides) hydroxy-fonctionnels utilises en tant que resines thermoplastiques de separation
EP0479445B1 (fr) Polyétheramines à fonctions hydroxyl utilisées comme couche barrière pour des matériaux sensibles à l'oxygéne
AU643173B2 (en) Hydroxy-functional polyesters as thermoplastic barrier resins
US5149768A (en) Hydroxy-functional poly(ether sulfonamides) as thermoplastic barrier resins
US5115075A (en) Amide and hydroxymethyl functionalized polyethers as thermoplastic barrier resins
US20080081883A1 (en) Polyester Polyols Derived From 2,5-Furandicarboxylic Acid, and Method
US5686551A (en) Hydroxy ether polymers as thermoplastic barrier resins
US5814373A (en) Heat-resistant hydroxy-functional polyethers as thermoplastic barrier resins
US5218075A (en) Amide and hydroxymethyl functionalized polyethers as thermoplastic barrier resins
US3245950A (en) Epoxy resin compositions and cured products obtained therefrom
US2279752A (en) Polymeric material
US6288208B1 (en) Highly branched oligomers, process for their preparation and applications thereof
US5852163A (en) Process for preparing hydroxy-functionalized polyesters
US5025100A (en) Liquid amine terminated derivatives of diglycidyl ethers
US6051294A (en) Heat-resistant hydroxy-functional polyethers as thermoplastic barrier resins
EP0470180B1 (fr) Poly(amide ether) hydroxy-fonctionnels utilises en tant que resine thermoplastique a effet barriere
US4713428A (en) Branched polyesters
US2915485A (en) Process for preparing flexible resinified products from polyepoxides and resulting products
US5097070A (en) High molecular weight trifunctional polyoxyethylene amines
US5091574A (en) Polyoxyethylene diamine derivatives of diglycidyl ethers
US3377316A (en) Polyhydroxyaminoureas and method of making same
EP1028989A1 (fr) Polymeres hydroxy ether en tant que resines haute barriere thermoplastiques

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 19911022

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): BE CH DE FR GB IT LI NL SE

A4 Supplementary search report drawn up and despatched

Effective date: 19920522

AK Designated contracting states

Kind code of ref document: A4

Designated state(s): BE CH DE FR GB IT LI NL SE

17Q First examination report despatched

Effective date: 19950526

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): BE CH DE FR GB IT LI NL SE

ET Fr: translation filed
REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REF Corresponds to:

Ref document number: 69030084

Country of ref document: DE

Date of ref document: 19970410

ET Fr: translation filed

Free format text: CORRECTIONS

REG Reference to a national code

Ref country code: CH

Ref legal event code: NV

Representative=s name: FIAMMENGHI-FIAMMENGHI

ITF It: translation for a ep patent filed

Owner name: ING. A. GIAMBROCONO & C. S.R.L.

REG Reference to a national code

Ref country code: CH

Ref legal event code: PFA

Free format text: THE DOW CHEMICAL COMPANY,2030 DOW CENTER ABBOTT ROAD P.O. BOX 1967,MIDLAND MICHIGAN 48674 (US) -DANN IN- THE DOW CHEMICAL COMPANY,2030 DOW CENTER,MIDLAND, MI 48674 (US)

RAP4 Party data changed (patent owner data changed or rights of a patent transferred)

Owner name: THE DOW CHEMICAL COMPANY

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
NLT2 Nl: modifications (of names), taken from the european patent patent bulletin

Owner name: THE DOW CHEMICAL COMPANY

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: SE

Payment date: 20010209

Year of fee payment: 12

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 20010515

Year of fee payment: 12

REG Reference to a national code

Ref country code: GB

Ref legal event code: IF02

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20020427

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20020430

EUG Se: european patent has lapsed

Ref document number: 90907828.9

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20030307

Year of fee payment: 14

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20030312

Year of fee payment: 14

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 20030314

Year of fee payment: 14

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: CH

Payment date: 20030319

Year of fee payment: 14

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20030331

Year of fee payment: 14

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20040426

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20040430

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20040430

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20041101

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20041103

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20040426

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20041231

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee

Effective date: 20041101

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED.

Effective date: 20050426